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Li was born in 1950 in Lianshui County, Jiangsu province, to Li Gancheng (李干成), a Communist Party official and later vice mayor of Shanghai; his mother is Lü Jiying (吕继英), a Communist revolutionary from Shuyang County in northern Jiangsu province; he was the fourth son among their seven children. He was named Yuanchao (援朝) after the "campaign to aid North Korea;" he would change the characters of this name later in life while maintaining the pronunciation. Li attended Nanyang Model High School in Shanghai, where he graduated in 1966, shortly prior to the Cultural Revolution. During the Cultural Revolution, he worked in Dafeng County, Jiangsu, performing manual labour.[3]

In 1972, Li was recommended to enter East China Normal University to study mathematics. He then worked as a teacher at the Nanchang Secondary School in Shanghai, then an instructor at the industry vocational college of Luwan District in Shanghai. After the resumption of the National College Entrance Examination Li was admitted to pursue a master's degree from Fudan University in mathematics. He joined the Communist Party of China in June 1978. In 1982, after graduating, he stayed at Fudan to teach as a lecturer and held a leadership position in the Communist Youth League organization of the university.

In 1983, Li was elevated on recommendation from then Shanghai party chief Chen Pixian to head the Shanghai Communist Youth League organization at age 33. Shortly thereafter he became a member of the Central Secretariat of the Communist Youth League, in charge of propaganda and ideology. He served in the post until 1990. During his time at the Youth League, Li obtained through part-time study a master's degree in in economic management from Peking University under the supervision of economist Li Yining, and a doctoral degree (also on a part-time basis) in law from the Central Party School. In 1993, he was named deputy head of the State Council Information Office. In 1996, he became Vice Minister of Culture. He pursued mid-career training at the John F. Kennedy School of Government at Harvard University in 2002.[4]

Li was elevated to Deputy Party Secretary of Jiangsu province and concurrently party chief of the provincial capital Nanjing in 2001. In October 2001, a mere month after he took office, Li garnered attention by firing several municipal officials accused of sexually harassing female hotel employees.[5]

At the 16th Party Congress held in 2002, Li failed to secure a seat to the Central Committee, and was elected only an alternate member; however, at the time of the election, Li had already been agreed upon by senior party leaders to serve in the top post in Jiangsu, causing an awkward and rare situation where Li would serve as a party chief of a major province without holding a full seat on the Central Committee.[6]

Li served as the Communist Party Provincial Committee Secretary for Jiangsu between 2002 and 2007. During his tenure in Jiangsu, Li assessed local officials in terms of performance measured by social and environmental factors, as opposed to purely economic ones.[7] In response to the corruption case of Xu Guojian, the head of the provincial Organization Department, Li said, "Jiangsu is beginning the biggest anti-corruption drive since the founding of the People's Republic."[8]

In March 2013, Li was elected to be the Vice President. The post of Vice-President had been held since 1998 by the top-ranked Secretary of the party's Secretariat; Li's selection as Vice President broke this fifteen-year convention; this meant Li was also the first Vice-President without a seat on the Politburo Standing Committee since 1998.[10] Since taking on the office, which is largely ceremonial in nature, Li has played a major role in foreign affairs. He served as the deputy leader of the Foreign Affairs Leading Group, the main foreign affairs coordination body of the Communist Party, and the deputy leader of the Central Coordination Group for Hong Kong and Macau Affairs. Li was the most senior Chinese official to attend the state memorial of South African leader Nelson Mandela and the state funeral of Lee Kuan Yew.